KR19980076753A - Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound and preparation method thereof - Google Patents

Abstract

Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound represented by the following Chemical Formula 1 may be used to add flame retardancy and heat resistance to plastic resins. By providing a novel flame retardant and a novel method of making it, the problem of removing phosphorus oxychloride and the production of undesirable oligomers during the conventional process of making the flame retardant are solved.

Description

Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound and preparation method thereof

[Industrial use]

The present invention relates to a flame retardant and a method for preparing the same, and more particularly to a novel organophosphorus compound which can be used to add flame retardancy and heat resistance to a plastic resin. A 1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound and a method for producing the same.

[Formula 1]

[Prior art]

Recently, regulations on combustibility of rubber, fiber, paper, and other products have been tightened, starting with plastics. In particular, since various polymer materials possess many excellent properties, they are used in a wide range of fields such as electric, electronic parts, vehicle parts, aircraft, and ships. For this reason, the necessity for flame retardation of these has been increased at home and abroad.

In general, organophosphorus compounds have been known as flame retardants having a relatively good flame retardant effect, but has been pointed out as a problem of somewhat high volatility and low heat resistance. In particular, newly developed high-performance plastics, such as engineering plastics or super-engineering plastics, have a demand for heat resistance of flame retardants because the processing temperature is around 300 ° C.

US Patent Nos. 2,520,090 and 4,134,876 disclose methods for preparing aromatic diphosphate oligomer phosphorus flame retardants by reacting phosphorus oxychloride with dihydric phenol compounds such as Formula 4 and monohydric phenol compounds such as Formula 5 have. The patent has the disadvantage of removing unreacted phosphorus oxychloride and also the disadvantage of producing large quantities of undesirable oligomeric products.

[Formula 4]

Examples of the compound of formula 4 include resorcinol, hydroquinone and the like.

[Formula 5]

Wherein R ₁ and R ₂ are an alkyl group having 1 to 8 carbon atoms, or when R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 8 carbon atoms.

EP 613,902 discloses a process for preparing aromatic diphosphate oligomeric phosphorus flame retardants by reacting phosphorus oxychloride with monohydric phenol compounds such as Formula 5 and dihydric phenol compounds such as Formula 4. The patent has a disadvantage in that the reaction intermediate must be purified after reacting the oxychloride and the monohydric phenol compound in order to suppress the formation of undesirable oligomers.

U.S. Patent No. 5,420,327, European Patent No. 509,506, and Japanese Patent Publication No. 2,552,780 react the phosphorus oxychloride with the monohydric phenol compound and then react with the dihydric phenol compound to obtain a powdered aromatic di A process for the preparation of phosphate phosphorus flame retardants is disclosed. It is known here that flame retardancy and heat resistance are superior to known non-halogen phosphorus flame retardants such as triphenylphosphate (TPP) and resorcinol diphosphate (RDP). However, resin compositions such as home appliances that generate a lot of heat not only have to be excellent in flame retardancy, but also have particularly high heat resistance, which has disadvantages that fall short of the level.

The present invention has been made to solve the above problems of the prior art, an object of the present invention is first, a flame retardant resin composition, such as polycarbonate resin, ABS resin, styrene copolymer having excellent flame resistance and particularly excellent heat resistance And aromatic diphosphate compounds used as flame retardants for polyolefin resins and the like.

Second, the present invention provides a method of making a high purity compound of more than 99.5% by giving a steric hindrance effect to the monohydric phenol compound to solve the problem of removing the phosphorus oxychloride during production and the production of undesirable oligomers will be.

Third, another object of the present invention is to provide an aromatic diphosphate compound into which a compound containing a tertiary butyl group is introduced through a chemical mixing method to add heat resistance.

[Means for solving the problem]

The present invention has the following configuration to achieve the above object of the present invention.

In the present invention, a bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound for a flame retardant represented by the following general formula (1) is provided.

[Formula 1]

In the present invention, a bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound represented by the following Chemical Formula 2 is provided using a type of aryl compound as resorcinol. .

[Formula 2]

In addition, a bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound represented by the following Chemical Formula 3 is provided by using a hydroquinone as a kind of the aryl compound.

[Formula 3]

In the present invention, the phosphorus oxychloride is reacted with a different compound represented by the formula (5) under a catalyst to produce a chlorophosphate reaction intermediate represented by the formula (6) and the reaction intermediate is reacted with a compound represented by the formula (4) under a catalyst It provides a method for producing a bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound comprising the step of producing a compound represented by the formula (1).

[Formula 4]

[Formula 5]

In Formula 5, R ₁ and R ₂ are alkyl groups having 1 to 8 carbon atoms, or when R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 8 carbon atoms.

[Formula 6]

In Formula 6, R ₁ and R ₂ are alkyl groups having 1 to 8 carbon atoms, or when R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 8 carbon atoms. In addition, when R ₁ 'and R ₂ ' is an alkyl group having 1 to 8 carbon atoms, or R ₁ 'is hydrogen, R ₂ ' is an alkyl group having 1 to 8 carbon atoms.

In preparing the chloropropate reaction intermediate represented by Formula 6, it is preferable to react different monohydric compounds step by step under a suitable catalyst.

The compound represented by the formula (4) is preferably resorcinol or hydroquinone.

The present invention can add heat resistance by introducing a compound containing a tertiary butyl group through a chemical mixing method. It also provides a method of controlling phosphorus content by combining different monohydric phenolic compounds. In the first reaction step, a molecule of 2,4-bis (1,1-dimethylethyl) phenyl, which gives steric hindrance effect to phosphorus oxychloride, is reacted to obtain a high purity of [2.4-bis (1,1-dimethyl) of 99.7% or more. In the second step after the preparation of ethyl)] phenyl dichlorophosphate, 2,6-dimethylphenol is a monohydric compound that is more reactive to this intermediate and has a lower molecular weight than 2,4-bis (1,1-dimethylethyl) phenol. [2,4-bis (1,1-dimethylethyl) phenyl-2,6- with a higher phosphorus content than the intermediate to which 2 moles of 2,4-bis (1,1-dimethylethyl) phenol was reacted by reacting Dimethylphenyl] chloro phosphate can be obtained. By using different monohydric phenols in combination in one molecule, a method of controlling phosphorus content of a compound is provided.

The following presents a preferred embodiment to aid the understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

EXAMPLE

The manufacturing method for the present invention is as follows.

Example 1: Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenol] resorcinol diphosphate

A well-dried flask was attached with a thermometer, a cooling condenser and a stirrer, and heated with 268.2 g of 2,4-bis (1,1-dimethylethyl) phenol, 2.0 g of magnesium chloride, and 100 g of xylene. When the temperature of the reaction solution reached 150 ℃ 199.3g of phosphorus oxychloride was injected over 1 hour. Hydrochloric acid gas generated at this time was collected by water. After the injection of phosphorus oxychloride, the reaction was continued at 150 ° C. After the generation of hydrochloric acid gas, the reaction solution was heated to 180 ° C., and aged for 4 hours to obtain [2,4-bis (1,1-dimethylethyl) phenyl] dichlorophosphate.

When the temperature of the dichlorophosphate reaction intermediate obtained in step 1 was cooled to 70 ° C and 158.9 g of xylenol and 2.0 g of magnesium chloride were added thereto, the reaction temperature was gradually increased to stop the generation of hydrochloric acid gas at 150 ° C. The reaction was carried out until. After the generation of hydrochloric acid gas, the reaction solution was heated to 180 ° C. and aged for 4 hours to obtain [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] chlorophosphate.

In the state where the temperature of the chlorophosphate reaction intermediate obtained in step 2 was cooled to 70 ° C., 71.6 g of resorcinol and 3.0 g of magnesium chloride were added thereto, and the reaction solution was heated to proceed at 150 ° C. Hydrochloric acid gas generated at this time was collected by water. After generation of hydrochloric acid gas was completed, the reaction solution was heated to 180 ° C. and aged for 4 hours. After completion of the reaction, to remove the catalyst component and impurities, washed with 400g of 5% hydrochloric acid solution and then again with water. And product crystal | crystallization precipitated while cooling to room temperature. The crystals were filtered, washed with 500 g of methanol, and dried under reduced pressure to obtain 534 g of a white crystalline powder having a melting point of 45 ° C. The purity of the compound obtained as a result of GPC analysis was 99.6%. The structure of the obtained compound was identified by infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR). IR analysis was carried out using Fourier transform infrared (FT-IR, BRUKER IFS66) in a mixed plate with potassium bromide. Measurement results are C = C stretching of the phenyl group, at a frequency 1496㎝ ^-1, 1084㎝ ^-1 as shown in the first absorption band, 1363㎝ ^-1, CH ₃ absorption band deformation, 1308㎝ with tertiary butyl groups in 1399㎝ ^{-1 The} P = O stretching band at ^-1 and the stretching band of PO-Ar at 1130 cm ^-1 are shown.

¹ H NMR analysis was performed using deuterated chloroform as solvent and BRUKER DRX 400 using CDCl ₃ 7.24 as internal standard. The measurement result δ is 1.28 (18H, s), 1.34 (18H, s), 2.3 (12H, s), 7.01 (9H, m), 7.15 (3H, m), 7.36 (2H, dd), 743 (2H, It was confirmed that d) has the structure shown in formula (2).

Example 2: Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] hydroquinone diphosphate

Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6 having a melting point of 49 ° C. in the same manner as in Example 1, except that hydroquinone was substituted for resorcinol in Example 1; -Dimethylphenyl] 530 g of hydroquinone diphosphate was obtained. The purity of the compound obtained as a result of GPC analysis was 99.5%. As a result of IR analysis on the obtained compound, the C = C stretching band of the phenyl group at the frequency of 1496 cm ^-1 and 1085cm ^-1 as shown in Fig. 2, and the CH ₃ deformation band of the tertiary butyl group at 1363cm ^-1 and 1399cm ^-1 , which showed a P = O stretching absorption band at 1307㎝ ^-1, stretching absorption band of PO-Ar in 1158㎝ ^-1.

¹ H NMR analysis result δ is 1.29 (18H, s), 1.34 (18H, s), 2.30 (12H, s), 7.01 (10, m), 7.14 (2H, dd), 7.37 (2H, dd), 7.44 (2H, d) confirmed the structure of Chemical Formula 3.

Comparative Example 1

Triphenylphosphate (TPP) (Junsei Co., Ltd. grade) was used as a flame retardant.

Comparative Example 2

Tetrakis [2,6-dimethylphenyl] resorcinol diphosphate was prepared according to US Pat. No. 5,420,327.

10 parts by weight of each of the flame retardants prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were mixed with 90 parts by weight of aromatic polycarbonate and 10 parts by weight of ABS, and then the cylinder temperature was adjusted to 230 to 260 ° C. using a twin screw extruder. After extruding, the pellet was cooled and cut to obtain a pellet. The specimen was prepared by injection at 240 to 260 ° C.

Table 1 shows the results of the flame retardancy test on the specimen prepared as described above.

TABLE 1

Flame retardant Flame retardant (UL94 1.6mm) Heat Deflection Temperature (50 ℃ / HR, 1㎏ / ㎠) Izod impact strength (kg, cm / cm 3.2mm) Tensile Strength (㎏ / ㎝ ² ) Example 1 V ₀ 128 61 610 Example 2 V ₀ 131 60 620 Comparative Example 1 (TPP) V ₂ 106 50 550 Comparative Example 2 V ₁ 118 51 590

Bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] resorcinol diphosphate compound and bis [2,4, which are flame retardants prepared according to the present invention as shown in Table 1 above The -bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] hydroquinone diphosphate compound has a higher heat deformation temperature than the triphenyl phosphate and the known aromatic diphosphate phosphorus flame retardant used as a comparative example, and the impact strength and tensile Because of its high strength, it can be usefully used as a flame retardant having excellent flame resistance and heat resistance.

The aromatic diphosphate phosphorus-based flame retardant according to the present invention can be used as a flame retardant in polycarbonate resin, ABS resin, styrene copolymer, polyolefin resin and the like because it is particularly excellent in heat resistance as well as flame retardancy.

Claims (6)

A bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound for flame retardants represented by the following general formula (1). [Formula 1] The bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound according to claim 1, wherein the aryl compound is a resorcinol. [Formula 2] The bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound according to claim 1, wherein the aryl compound is represented by hydroquinone. [Formula 3] Reacting the phosphorus oxychloride with a compound represented by the formula (5) under a catalyst to produce a dichlorophosphate reaction intermediate; Reacting the reaction intermediate with a compound represented by Formula 5 under a catalyst to produce a chlorophosphate reacted intermediate represented by Formula 6; Reacting the intermediate with a compound represented by Formula 4 under a catalyst to produce a compound represented by Formula 1; A method for producing a bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound comprising a step. [Formula 4] [Formula 5] [Formula 6] In Formula 5, when R ₁ and R ₂ are an alkyl group having 1 to 8 carbon atoms, or R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 8 carbon atoms and in Formula 6, R ₁ and R ₂ are 1 to 8 carbon atoms. When R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 8 carbon atoms and R ₁ 'and R ₂ ' are an alkyl group having 1 to 8 carbon atoms, or when R ₁ 'is hydrogen, R ₂ ' is It is a C1-C8 alkyl group. The bis [2,4-bis (1,1-dimethylethyl) according to claim 4, wherein the bis [2,4-bis (1,1-dimethylethyl) is reacted stepwise under different catalysts in the preparation of the chlorophosphate reaction intermediate represented by Chemical Formula 6. Phenyl-2,6-dimethylphenyl] aryl diphosphate compound. The preparation of bis [2,4-bis (1,1-dimethylethyl) phenyl-2,6-dimethylphenyl] aryl diphosphate compound according to claim 4, wherein the compound represented by Chemical Formula 4 is resorcinol or hydroquinone. Way.